JPS5827106B2 - Method for manufacturing aluminum laminates - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an aluminum laminate, and more specifically to producing a sealed package for retort sterilization that has excellent flavor retention properties and delamination resistance after retort sterilization. The present invention relates to a method for manufacturing a laminate that can be advantageously used for.

Conventionally, for use in sealed packages for retort sterilization, a crystalline olefin resin layer for heat sealing is provided on one surface of an aluminum foil or sheet, and a heat-resistant resin layer such as polyethylene terephthalate is provided on the other surface. Laminated sheets are widely used.

These laminated sheets are stacked together and then heat-sealed to form a bag, filled with food or other contents, deaerated and sealed, and then heated and sterilized in a sterilizer called a retort. It shall be a storable package.

The crystalline olefin resin used as the sealant and inner surface material is generally inert, and the package is subjected to harsh heat sterilization treatment, so urethane adhesives are used exclusively to bond the olefin resin layer and aluminum foil or sheet. This is done using a thermosetting adhesive such as (incyanate adhesive) or epoxy adhesive.

Although the above-mentioned thermosetting adhesives are generally satisfactory for the purpose of forming adhesive bonds with excellent heat resistance and hot water resistance, they are still unsatisfactory for the purpose of preserving the flavor of food contents after retort sterilization. It wasn't a kimono.

That is, thermosetting resins are complex resin compositions containing uncondensed monomers and relatively low molecular weight condensation polymers, and
In the above-mentioned package, the thermosetting adhesive layer is always located inside the impermeable metal aluminum layer, so harsh treatments such as retort sterilization can cause decondensation of the uncondensed substances and low molecules mentioned above. The coalescence tends to migrate into or interact with the food contents.

Further, the above-mentioned thermosetting adhesive is generally provided in a diluted form with an organic solvent such as toluene, ethyl acetate, methyl, or ethyl ketone.

When laminating aluminum foil and crystalline olefin resin film using such a thermosetting adhesive, the process of applying the adhesive to the aluminum foil, drying the solvent with hot air, and then performing pressure bonding and lamination is necessary. It will be done.

However, it is difficult to completely remove the organic solvent by open drying, and this residual organic solvent may migrate into the food contents by retort sterilization treatment and may significantly impede the flavor of the food contents.

Due to these reasons, although packages made of laminated sheets made by bonding a crystalline olefin resin layer and aluminum foil etc. with a thermosetting adhesive have excellent preservability, they are not effective in retaining the flavor of the food they contain. It was still not completely satisfactory.

Among various thermoplastic adhesives, the present inventors selected a modified olefin resin having a crystallinity of 15 to 95% and a carbonyl group content in the range of 1 to 600 meq/1009 polymer. The crystalline olefin resin is melt-extruded simultaneously with the crystalline olefin resin as a multilayer structure, and this multilayer extrudate is fused to aluminum foil, etc. in a position where the modified olefin resin layer contacts the aluminum foil, etc. It is possible to introduce an adhesive bond with excellent heat resistance, hot water resistance, impact resistance, etc. between the layer and aluminum foil, etc., and it is possible to obtain a laminate that can withstand retort sterilization. It has been found that the flavor retention characteristics of the food contents can be significantly improved by using the composition as a sealed package for food products.

An object of the present invention is to provide a method for manufacturing a laminate in which an impermeable aluminum foil or the like and a heat-sealable crystalline olefin resin layer are fused and bonded via an adhesive layer made of a modified olefin resin. .

Another object of the present invention is to form an adhesive bond between an aluminum foil or the like and a crystalline olefin resin layer that can withstand retort sterilization treatment, and furthermore, this adhesive layer can protect the contents when the package is sealed. To provide a method for obtaining a laminate that does not adversely affect flavor.

Still another object of the present invention is to provide a new method for easily manufacturing a laminate by directly fusing a co-melt extrudate of a crystalline olefin resin and a modified olefin resin to aluminum foil or the like.

According to the present invention, the crystalline olefin resin layer has a crystallinity of 15 to 95% and a carbonyl group content of 1 to 60%.
0meq/100? a step of co-melting extruding a modified olefin resin layer having a polymer concentration and the constituent olefin units of the same type as the crystalline olefin resin as a multilayer structure; There is provided a method for producing a laminate, which comprises the step of fusing the aluminum foil or sheet in a state adjacent to the aluminum foil or sheet.

The invention will be explained in detail below.

In FIG. 1 showing the cross-sectional structure of a laminate produced by the method of the present invention, a laminate sheet 1 is made of aluminum foil or a sheet 2,
It consists of a crystalline olefin resin layer 4 bonded to at least one surface of the aluminum foil or sheet 2 via a modified olefin resin layer 3, and the other surface of the aluminum foil or sheet 2 includes:
It may have a heat-resistant resin layer 6 bonded via an adhesive layer 5 if desired.

An important feature of the present invention is that the adhesive for bonding the aluminum foil 1 and the crystalline olefin resin layer 4 has a crystallinity of 15 to 95%, particularly 40 to 80%, and a carbonyl group content of 1 to 95%. 600meq/100? Polymers, especially 10 to 300 meq/100? Selecting a modified olefin resin layer which is a polymer and whose constituent olefin units are substantially the same in amount as the crystalline olefin resin, and forming a laminate by simultaneous melt extrusion of the modified olefin resin and the crystalline olefin resin. The purpose of this method is to directly fuse this laminate with aluminum foil or the like.

First, if the crystallinity of the modified olefin resin is less than 15%, it is extremely difficult to form an adhesive bond between the crystalline olefin resin layer and the aluminum foil that can withstand retort sterilization. A sealed package produced using this laminate will easily cause delamination in a retort atmosphere of hot water or hot steam at a temperature higher than 100°C.

In addition, the carbonyl group content is 1 meq7100 ft
It is difficult to form a sufficient adhesive bond with aluminum foil with a modified olefin resin having a lower carbonyl group content than that of the polymer; It is again difficult to form a sufficient adhesive bond with the resin layer.

Furthermore, when the constituent olefin monomer of the modified olefin resin is different from that of the crystalline olefin resin,
After all, significant peeling between layers occurs during retort sterilization.

In contrast, according to the present invention, a modified olefin resin whose crystallinity, carbonyl group content, and type of constituent olefins are within the above-mentioned ranges is selected as the modified olefin resin, and this modified olefin resin is used as a crystalline olefin resin. By simultaneously melting and extruding the laminate as a laminate, and heat-sealing this laminate in a position where the modified olefin resin layer contacts the aluminum metal, a layer between the crystalline olefin resin layer and aluminum foil, etc. They succeeded in introducing an adhesive bond that is strong and can withstand hot water and steam.

In this specification, crystallinity refers to
Polymer Science (J, Polym, Sci,
) Volume 18, pp. 17-26, 1955 (S, L.

Aggarwal and G., D., Tiley.
) refers to the degree of crystallinity determined by the X-ray diffraction method.

In the present invention, the modified olefin resin is a carbonyl group-containing ethylenically unsaturated monomer known per se. Among those introduced into the chain, those that satisfy the above conditions are used.

Examples of the carbonyl group-containing ethylenically unsaturated monomer include carbonyl based on carboxylic acid, carboxylic acid salt, carboxylic acid anhydride, carboxylic acid ester, carboxylic acid amide or imide, aldehyde, ketone, etc. or a cyano (-C=N) group;
Hydroxy group; Ether group; Oxirane (-C-C-)
It is possible to use one type or a combination of two or more types of ethylene\1-based unsaturated monomers in combination with rings, etc., and suitable examples thereof are as follows.

A, ethylenically unsaturated carboxylic acid nialic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid.

B, ethylenically unsaturated carboxylic anhydride: maleic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, tetrahydrophthalic anhydride.

C, ethylenically unsaturated ester: ethyl acrylate, methyl methacrylate, Aku'J #
2-r-hexyl acid, mono- or di-ethyl maleate, vinyl acetate, vinyl propionate, γ-human Pxypropyl methacrylate, β-hydroxyethyl acrylate, glycidyl acrylate, glycidyl methacrylate, βN-ethylamino Ethyl acrylate.

D. Ethylenically unsaturated amide or imide: acrylamide, methacrylamide, maleimide.

E. Ethylenically unsaturated aldehydes or ketones: acrolein, methacrolein, vinyl methyl ketone, vinyl butyl ketone.

In the present invention, among the above-mentioned monomers, ethylenically unsaturated carboxylic acids and ethylenically unsaturated carboxylic anhydrides are particularly preferred, and these monomers may be used alone or in combination with other monomers. Used in combination to modify olefin resins.

These carbonyl group-containing monomers are bonded to the main chain or side chain of the olefin resin so that the concentration of polar groups is within the above range and the crystallinity of the modified olefin resin is at least 15%.

As olefins, ethylene, propylene, butene
1, pentene-114-methylpentene 1, etc., or a combination of two or more thereof, which satisfies the above-mentioned conditions.

In order to modify an olefin resin so as to satisfy the above-mentioned conditions, for example, in the case of graft treatment, an olefin resin with a degree of crystallinity higher than 15% is selected as the raw material olefin resin, and the olefin resin is It is necessary to carry out the grafting treatment under conditions such that the degree of crystallinity does not fall below 15%.

For this purpose, high-crystalline materials such as high-density polyethylene, tactical polypropylene, or ethylene-propylene copolymers are preferably used as the backbone polymer, and furthermore, the decrease in crystallinity is virtually unstoppable. Under such mild grafting conditions, medium density polyethylene or low density polyethylene with a crystallinity higher than 15% may also be used.

The above-mentioned grafting process can be carried out under conditions known per se, except for the above-mentioned limitations.

For example, a modified olefin resin can be easily obtained by bringing a backbone polymer derived from an olefin resin into contact with a carbonyl group-containing ethylenically unsaturated monomer in the presence of a radical initiator acid (. is a radical initiator). I can do it.

The backbone polymer and the monomer can be contacted in a homogeneous solution system, a solid-liquid or solid-quick homogeneous system, or a melt homogeneous system.

Examples of initiators include organic peroxides such as dicumyl peroxide, t-butyl hydroperoxide, dibenzoyl peroxide, and dilauroyl peroxide, and azonitriles such as azobisisobutyronitrile and azobisisopropionitrile. etc. are used in catalytic amounts known per se.

Examples of radical initiating means include ionizing radiation such as X-rays, γ-rays, and electron beams; ultraviolet rays or a combination of ultraviolet rays and a sensitizer; mechanical radical initiating means such as kneading (mastication) and ultrasonic irradiation. used.

For example, in a homogeneous solution reaction, an olefin resin, a monomer, and an initiator are dissolved in an aromatic solvent such as toluene, xylene, or tetralin to perform grafting, and the resulting modified olefin resin is recovered as a precipitate.

In addition, in a heterogeneous reaction, grafting is carried out by bringing the olefin resin powder into contact with the monomer or a diluted solution of the monomer under irradiation with ionizing radiation.

Furthermore, in homo-melt reactions, the blend of olefin resin, monomer, or even initiator is fed into an extruder or kneader.
etc. to obtain a modified olefin resin.

Even in these cases of collapse, the resulting modified olefin resin can be subjected to purification treatments such as washing and extraction in order to remove unpolymerized monomers, homopolymers, initiator residues, and the like.

Furthermore, the particle size of the produced modified olefin resin can be adjusted by subjecting it to the recrystallization operation in the aromatic solvent described above and changing the crystallization conditions at that time.

In this way, the modified olefin resin used in the present invention can be easily obtained.

Another example of the modified olefin resin having the above-mentioned carbonyl group content concentration is polyethylene oxide.

The oxidized polyethylene used in the present invention is a so-called oxidized polyethylene that satisfies the above-mentioned requirements, which can be obtained by oxidizing polyethylene or a copolymer mainly composed of ethylene in a melt or solution state, if desired. is used.

The molecular weight of the modified olefin resin used may be sufficient to form a film, and generally has a melt index (MI) of 0.2 to 30 f/lO, particularly 2 to 20 f/lO. /10 minutes is preferably used.

Still other examples of modified olefin resins include ionomers, that is, polymers obtained by neutralizing copolymers of olefins and ethylenically unsaturated carboxylic acids with metal ions such as Na, Zn, Ca, and amines. Also, copolymers of olefins and ethylenically unsaturated carboxylic acids, esters thereof, or vinyl esters can be mentioned.

In the present invention, the above-mentioned modified olefin resins can be used alone or in the form of a blend of two or more types.

Moreover, this modified olefin resin can also be used in the form of a blend with a crystalline olefin resin or a blend of these with an elastomer.

In any of these cases, the point is that the crystallinity, carbonyl group content, and main composition of the olefinic monomers of the final resin composition are within the ranges specified in the present invention.

Examples of the crystalline olefin resin include known olefin resins that can be heat sealed and withstand retort sterilization, such as low, medium to high density polyethylene tactical polypropylene, polybutene 114-methylpentene-1.
Polyolefins such as 1-functional tyrene to propylene copolymers or blends thereof are used.

In order to improve the impact resistance and, in some cases, the blocking properties of the polyolefin, a small amount of an elastomer such as polyisobutylene, phthyl rubber, styrene butadiene rubber, ethylene propylene rubber, etc. is added to the crystalline olefin resin, i.e.,
It can be blended in an amount of 1 to 30% by weight per crystalline olefin resin.

The aluminum foil or sheet generally has a thickness of 6 to 80 mm for use in flexible sealed packaging such as bag-shaped containers.
In the case of rigid or semi-rigid containers such as squeeze containers and press-formed containers, foils or sheets with a thickness of 9 to 500 microns are used.

Even if the surface of the aluminum foil or sheet is untreated,
Alternatively, it may be subjected to a known surface treatment.

For the purpose of the present invention, it is desirable to use an aluminum foil or sheet having an alumina hydrate layer of 10 to 1000 millimicrons, and a modified olefin resin layer is provided adjacent to the alumina hydrate layer. It is better.

A crystalline olefin resin layer can be provided on both surfaces of aluminum foil, etc. via a modified olefin resin layer, or a crystalline olefin resin layer can be provided on only one surface of aluminum foil, etc., and the other surface, A heat-resistant resin layer can be provided for protection.

As the heat-resistant resin layer, a thermoplastic resin or a thermosetting resin having a higher melting temperature or decomposition temperature than the above-mentioned crystalline olefin resin is used.

Heat-resistant thermoplastic resins include polyesters such as polyethylene terephthalate, nylon 6-nylon-6
- Polyamides, polycarbonates, cellulose esters, fluororesins, etc. as shown in 6. Examples of thermosetting resins include, for example, imide rings, imidazopyrrolone rings, imidazole rings, oxazole rings, oxacyazole rings, etc. in the molecular chain. Heat-resistant polymers containing a heterocyclic ring such as a thiazole ring, such as polyimide, polyamideimide, polyesterimide, polyamideimide ester, polyesteramideimide, polyimideimidazopyrrolone, etc., can be used.

Or in addition, epoxy/phenolic resin paint, phenolic resin paint, unsaturated polyester resin paint,
Oleogenous paints and the like can also be used.

Heat-resistant thermoplastic resins are easily available as unstretched or biaxially stretched films, and these films can be laminated onto aluminum foil or sheets using known adhesives such as epoxy adhesives and polyurethane adhesives. On the other hand, heat-insoluble heat-resistant resins are formed by applying a solution of a precursor polymer of these resins to the foil or sheet and then baking it.

According to the present invention, the above-described crystalline olefin resin layer and modified olefin resin layer are simultaneously melt-extruded as a multilayer structure.

This co-melt extrusion can be easily accomplished by using an extruder for the crystalline olefin resin and an extruder for the modified olefin resin, and extruding the molten resin streams from both extruders through a multilayer die.

As a multilayer die, a flat die or a circular die can be used, and co-extruded products can be coated directly on aluminum foil etc. by the itastrusion coating method using a flat die.
Alternatively, it can be formed into a film or sheet by a T-die method, a screw die method, an inflation film forming method, etc. before being applied to aluminum foil or the like.

When this multilayer structure is heat-sealed to aluminum foil or the like, the modified olefin resin layer in the multilayer structure is placed adjacent to the aluminum foil or the like.

In the extrusion coating method of the present invention, in order to improve interlayer adhesion between the aluminum foil or the like and the modified olefin resin layer, the aluminum foil or sheet is coated with the modified olefin resin before contacting with the modified olefin resin. It is preferable to maintain the temperature at a temperature equal to or higher than the Vicat softening point of the modified olefin resin to fuse the freshly extruded multilayer structure to the aluminum foil or sheet.

For this purpose, aluminum foil or the like is generally preheated by a heating mechanism known per se, and immediately before it comes into contact with the modified olefin resin layer to be extruded, the aluminum foil or the like is heated to a temperature equal to or higher than the Vicat softening point (TM) of the modified olefin resin, particularly preferably. The temperature should be from TM+10°C to 100°C below TM.

As the heating mechanism, any mechanism such as a heat roll, an infrared heater, various heating furnaces, direct flame heating, hot air blowing, high frequency induction heating, etc. can be used alone or in combination.

A laminated structure consisting of a modified olefin resin layer and a crystalline olefin resin layer is fused to aluminum foil or the like maintained at the above temperature using a pressure roller or the like to form a laminated sheet.

In order to maintain the temperature of the aluminum foil and the like at the above-described temperature, it is desirable that the surface temperature of the pair of pressure rollers used at this time be maintained at a temperature equal to or higher than the Vicat softening point of the modified olefin resin.

The produced laminate is passed over a cooling roller or allowed to cool naturally to form a laminate for packaging.

According to this aspect of the present invention, the aluminum foil or the like is heated to a temperature equal to or higher than the softening point of the modified olefin resin prior to contact with the modified olefin resin layer in the multilayer structure.
The modified olefin resin layer that comes into contact with aluminum foil, etc. is prevented from being rapidly cooled, and as a result, the mechanical properties of the modified olefin resin layer itself and the adhesive strength with aluminum foil, etc. can be maintained at a high level. .

In another embodiment of the extrusion coating method of the present invention, the freshly extruded multilayer structure is combined with the aluminum foil or sheet, and the modified olefin resin is temporarily adhered to the aluminum foil or sheet. A laminate is produced, and then this laminate is heated to a temperature equal to or higher than the Vicat softening point of the modified olefin resin.

As the heating mechanism, the one described above is used.

In still another aspect of the present invention, the laminate obtained by extrusion coating the preheated aluminum foil described above is further passed through a post-heating mechanism to perform post-heating, thereby increasing the adhesive strength. A laminate with extremely improved properties can be obtained.

Furthermore, the multilayer structure is formed into a film or sheet in advance, and the film or sheet and the aluminum foil or sheet are stacked so that the modified olefin resin layer faces the aluminum foil or sheet, The stacked body can then be pressed together at a temperature equal to or higher than the Vicat softening point of the modified olefin resin to form a product.

In the present invention, the thickness of the crystalline olefin resin layer in the multilayer structure is preferably 10 to 300 microns, particularly 30 to 100 microns, from the viewpoint of heat sealing the final laminate, while the modified olefin resin layer The thickness is preferably 1 to 50 microns, particularly 5 to 20 microns, from the viewpoint of adhesion.

Further, the layer configuration of the multilayer structure may be any layer arrangement as long as the condition that the crystalline olefin resin layer is located on one side and the modified olefin resin layer is located on the other side is satisfied.

For example, in order to further improve interlayer adhesion, the modified olefin resin layer has a carbonyl group content of 100 to 60 in the portion adjacent to the aluminum foil or sheet.
0meq/100? The highly modified olefin resin layer in the polymer range and the portion adjacent to the crystalline olefin resin layer have a carbonyl group content of 1 to 200 meq/10
0? It can have a multilayer structure with a low modified olefin resin layer in the range of polymers.

The thickness ratio of the highly modified olefin resin layer (a) and the low modified olefin resin layer (b) can vary from 1:9 to 9:1.

In addition, in order to improve the impact resistance of the laminated structure without reducing interlayer adhesion, a modified olefin resin containing the above-mentioned elastomer is added between the modified olefin resin layer and the crystalline olefin resin layer. Alternatively, a modified olefin resin layer may be formed into two layers, and an impact-reducing layer made of polyamide, copolyamide, polyester-polyether, polyester-polylactone, or the like may be interposed therebetween.

In the present invention, numerous advantages are achieved by coextruding the crystalline olefin resin layer and the modified olefin resin layer into a multilayer structure.

In other words, this co-extrusion method introduces an extremely strong and durable adhesive bond between the crystalline olefin resin layer and the modified olefin resin layer, and also improves the bond between the crystalline olefin resin layer and aluminum foil, etc. It becomes possible to significantly reduce the thickness of the modified olefin resin layer used in the laminate, thereby achieving significant advantages economically and in terms of the physical properties of the laminate.

That is, when forming a film or extrusion coating a modified olefin resin alone, making the thickness smaller than 10μ, especially smaller than 5μ ensures continuity and uniformity of the thickness of the film. It is extremely difficult from this point of view.

On the other hand, according to the present invention, the modified olefin resin layer is extruded while being supported by the crystalline olefin resin layer, which improves the continuity and thickness of the film compared to the case of forming a single film. It is possible to reduce the thickness to about 1 micron while ensuring uniformity, which not only significantly reduces manufacturing costs, but also improves oil resistance due to the presence of modified olefin resin. This makes it possible to significantly reduce the tendency of decline, etc.

Furthermore, in the present invention, since the adhesive resin and the inner surface resin are molded by co-extrusion, the process is simplified and there are significant economic advantages.

The invention is illustrated by the following example.

Example 1 A biaxially stretched polyethylene terephthalate film with a thickness of 12μ and an aluminum foil with a thickness of 9μ were laminated using a urethane adhesive.

Next, the average carbonyl group concentration of isotactic polypropylene grafted with maleic anhydride is 140 m
-eq/1001 polymer, crystallinity 65%, melting point 1
59℃, Vicat softening point 141℃, melt index (MI) 10.0? /l 0m1n of modified polypropylene was put into a first tube having a screw with a diameter of 50mmφ.
Using an extruder, the density is 0.90ff/cr? i, isotactic polypropylene with a melting point of 162 °C and an MI of 9.0 P/10ynIn was heated to a temperature of 220 °C using a second extruder with a screw of diameter 651 mφ.
Co-extrusion is carried out from a T-shaped two-layer double die with a width of 650 mm maintained at °C, and this molten two-layer laminate and the aluminum laminate previously heated and maintained at 200 °C by a high-frequency induction heating device are heated to is held at 180℃ and the diameter is 4
0 (Jnmφ and 200iiφ pair of rolls,
The mixture was then cooled to room temperature using a cooling roll having a diameter of 400 mm to obtain a laminate sheet having a configuration of 12 μ polyethylene terephthalate layer/9 μ aluminum foil/10 μ polypropylene layer/60 μ polypropylene layer.

When the peel strength between the aluminum foil and polypropylene layer of this laminated sheet was measured, it was 1020? 71.
It was 5 cm.

Next, after immersing this laminated sheet in boiling water for 120 minutes,
When peel strength was measured, no decrease in strength was observed.

Furthermore, this laminated sheet was placed in heated steam at 135°C for 1 hour.
When treated for 0 minutes, no peeling between the layers was observed, and no decrease in adhesive strength was observed.

Example 2 A biaxially stretched polyethylene terephthalate film with a thickness of 12μ and an aluminum foil with a thickness of 20μ were laminated using a urethane adhesive.

Next, a carbonyl group concentration of 310 m-ep/10011 polymer was obtained by grafting maleic anhydride and itaconic anhydride at a molar ratio of 3:l to an ethylene-propylene block copolymer with an ethylene content of 5 mol%, Crystallinity is 6
0%, melting point 152°C, Vicat softening point 139°C,
50% by weight of modified propylene copolymer with MI of 12.0 P/10tnin, density of 0.90 P/i, and melting point of 15
4℃, MI is l Q, Q f / l □min, x
A friend product with 50% by weight of an ethylene-propylene block copolymer having a tyrene content of 5 mol% was prepared using a first extruder having a screw with a diameter of 50 mm and a density of 0.90 g/-1. Melting point is 157℃, MI is 9.0? /
An ethylene-propylene block copolymer with an ethylene content of 10wn and an ethylene content of 4 mol% was produced using a second extruder having a screw with a diameter of 65 mm, and a T-shaped extruder with a width of 650 mm maintained at a temperature of 225 °C. Co-extrusion was carried out from a double gooey for two layers, and this molten two-layer laminate was heated and held at 200°C in advance using a heating oven and a high-frequency induction heating device.The temperature was maintained at 170°C. is crimped with a pair of rolls of 400 mm diameter and 200 mm diameter, and then cooled to room temperature using a cooling roll with a diameter of 400 mm diameter, resulting in a composition of 12μ polyethylene terephthalate layer/20μ aluminum foil/15μ modified propylene layer. A laminated sheet having a polymer blend layer and a 155μ propylene copolymer layer was obtained.

The peel strength between the aluminum foil and the propylene copolymer layer of this laminated sheet was measured and was 1080 g/1.
It was 5crn.

Moreover, when the same boiling water treatment and heated steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength was observed.

Comparative Example 1 In Example 1, when unmodified polypropylene was used instead of maleic anhydride-modified polypropylene, there was no adhesiveness to aluminum foil at all, and a laminate could not be obtained.

Comparative Example 2 When a maleic anhydride-modified polypropylene having an average carbonyl concentration of 800 m-eq/1009 polymer was used as the modified polypropylene in Example 1, the adhesion between the modified polypropylene layer and the polypropylene layer was poor. Met.

Comparative Example 3 In Example 1, when the laminated aluminum sheet and the pressure roll were laminated at a heating temperature of 100°C, the adhesion was poor and a laminate for retort sterilization packaging could not be obtained.

Comparative Example 4 In Example 2, when a maleic anhydride- and itaconic anhydride-modified propylene copolymer with a carbonyl concentration of 0.8 m-eq/100 ft polymer was used as the modified propylene copolymer, adhesion to aluminum foil was poor. It was not possible to obtain a laminate for retort sterilization packaging due to poor properties.

Comparative Example 5 In Example 2, instead of the modified propylene copolymer, a polymer in which maleic anhydride was grafted onto high-density polyethylene had an average carbonyl group concentration of 130 m-eq/100f, a crystallinity of 68%, and a melting point of 128. ℃, Vicat softening point is 98℃, MI is 5.0? /10m1n modified polyethylene was used.
The adhesive strength between the blend layer and the propylene copolymer layer was insufficient, making it unsuitable as a laminate for retort sterilization packaging.

Example 3 A biaxially stretched polyethylene terephthalate film with a thickness of 12 μm and an aluminum foil with a thickness of 30 μm whose surface had been treated with boehmite were laminated using a urethane adhesive.

Next, maleic anhydride and fumaric acid were added to an ethylene-propylene random copolymer with an ethylene content of 3 mol%.
The concentration of carbonyl groups grafted with a molar ratio of :1 is 14
m-eq/100f polymer, crystallinity 55%, melting point 147°C, Vicat softening point 137°C, MI 12, O
S' 710m1n modified propylene copolymer 70% by weight, density 0.90P/i, melting point 154℃, MI 1
0.0? /10m1n, a blend with 30% by weight of an ethylene-propylene block copolymer with an ethylene content of 5 mol% was produced using a first extruder having a screw with a diameter of 50 mmφ, and the density was 0.90 g/cvi. Isotactic polypropylene with a melting point of 157°C and an MI of 9.0 was heated using a second extruder having a screw with a diameter of 65mm, and a T of width 650cm was kept at a temperature of 220°C.
Co-extrusion is carried out from a double die for two layers, and this molten two-layer laminate is preheated for 20 minutes using an oven and high-frequency induction heating device.
The aluminum laminate heated and held at 0°C is heated to 170°C and has a diameter of 400■φ and 200ii.
By pressing with a pair of φ rolls and then cooling to room temperature with a cooling roll having a diameter of 400 φ, the composition is 12μ polyethylene terephthalate layer/30μ aluminum foil/10μ modified propylene copolymer blend layer 7
A laminated sheet of 60μ isotactic polypropylene layers was obtained.

The peel strength between the aluminum foil and the propylene copolymer layer of this laminated sheet was measured and was 1730? /
It was 1.5 cIrL.

Moreover, when the same boiling water treatment and heated steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength was observed.

Example 4 A 12μ thick biaxially oriented polyethylene terephthalate film with gravure printing on one surface and a 9μ thick film
aluminum foil and were laminated using a urethane adhesive so that the printed side was on the inside.

Next, a polymer with a carbonyl group concentration of 490 m-eq/1001, in which maleic anhydride and citraconic anhydride were grafted at a molar ratio of 2:1 to an ethylene propylene block copolymer with an ethylene content of 5 mol%, was prepared. degree of conversion is 52%
, melting point is 147℃, Vicat softening point is 137℃, MI is 12.0? Using a first extruder having a screw with a diameter of 50 mm, maleic anhydride and citraconic anhydride were added to an ethylene-propylene block copolymer with an ethylene content of 5 mol%. is a carbonyl group concentration of 110 m-eq/100f polymer grafted in a molar ratio of 2:l, crystallinity of 62%
, melting point is 153℃, Vicat softening point is 141'C1M
A modified propylene copolymer with an I of 12.0 g/10 was processed using a second extruder having a screw with a diameter of 50 mm.
Density is 0.90 g/d, melting point is 157°C, MI is 9.0
The diameter of ethylene propylene block copolymer with ethylene content of 4 mol% is 6511LWLφ
Using a third extruder with a screw of
Co-extrusion was performed from a T-shaped three-layer triple die with a width of 650 mm kept at 0°C, and this molten three-layer laminate and the aluminum laminate previously heated and maintained at 190°C using an oven and a high-frequency induction heating device were coextruded. was pressed together with a pair of rolls with diameters of 400mmφ and 200mmφ maintained at a temperature of 180°C, and then cooled to room temperature using a cooling roll with a diameter of 400mmφ, resulting in a composition of 12μ polyethylene terephthalate layer/9μ aluminum. A laminated sheet of foil/4μ highly modified propylene copolymer layer/4μ low modified propylene copolymer layer/65μ propylene copolymer layer was obtained.

The peel strength between the aluminum foil and the propylene copolymer layer of this laminated sheet was measured and was 1620 g/1.
It was 5CrfL.

In addition, when the film was subjected to boiling water treatment and heated steam treatment in the same manner as in Example 1, no decrease in adhesive strength or peeling between the layers was observed.

Example 5 A biaxially stretched polyethylene terephthalate film with a thickness of 12μ and an aluminum foil with a thickness of 9μ were laminated using a urethane adhesive.

Next, maleic anhydride and fumaric acid were added to an ethylene-propylene block copolymer with an ethylene content of 4 mol%.
The carbonyl group concentration grafted with a molar ratio of :1 is 26
0m-eq/100g polymer, crystallinity 59%,
Melting point is 151'C, Vicat softening point is 138'C, MI
Using a first extruder having a screw with a diameter of 501 Lmφ, a modified propylene copolymer having a diameter of 12.0 P710 m1n was used, and 40% by weight of the modified propylene copolymer was
and density is 0.90 y/cnt, melting point is 157℃, MI
9. oy/iom=, a blend of 60% by weight of an ethylene-propylene block copolymer with an ethylene content of 4 mol% was produced using an extruder having a screw with a diameter of 501 mφ to produce the ethylene-propylene block copolymer 93. Weight% and average molecular weight are 100,000, ethylene content is 62 mol%, phlopylene content is 35 mol%, l・4-
A blend of 7% by weight of ethylene-propylene-diene copolymer rubber (EPDM) containing 3% by mole of hexadiene was maintained at a temperature of 220°C using a third extruder having a screw with a diameter of 651 mφ. Co-extrusion is carried out from a T-shaped three-layer triple die with a sagging width of 650 mm, and this molten three-layer laminate is heated in an oven and high-frequency induction heating device in advance.
The aluminum laminate heated and held at 00°C is heated to 190°C and has a diameter of 400 wφ and 200 m.
After crimping with a pair of rolls of 1φ, further crimping with another pair of rolls with a diameter of 200gmφ maintained at a temperature of 200°C, and then cooling to room temperature with a cooling roll with a diameter of 400mmφ. A laminated sheet of 12μ polyethylene terephthalate layer/9μ aluminum foil, 15μ modified propylene copolymer layer/10μ modified propylene copolymer blend layer, and 155μ propylene copolymer layer was obtained.

When the peel strength between the aluminum foil and the propylene copolymer layer of this laminated sheet was measured, it was found to be 1310 S'
/1.5 crrL.

Moreover, when the same boiling water treatment and heated steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength was observed.

Example 6 A biaxially stretched polyethylene terephthalate film with a thickness of 12μ and an aluminum foil with a thickness of 9μ were laminated using a urethane adhesive.

Next, a polymer with a carbonyl group concentration of 130 m-eq/lOOg was prepared by grafting maleic anhydride onto high-density polyethylene, a crystallinity of 68%, a melting point of 128°C, a Vicat softening point of 98°C, and an MI of 5. Using a first extruder having a screw with a diameter of 50 mm, modified polyethylene with a density of 0.955 t/c11 t, a melting point of 130°C, and an MI of 2.0 f/10 wisteria was used. Density polyethylene 92% by weight, average molecular weight 800,000, density 0.92f
A blend of 8% by weight of polyisobutylene/rubber of This molten two-layer laminate and the aluminum laminate previously heated and maintained at 200°C using an oven and an infrared heater were heated to a temperature of 150°C.
By pressing with a pair of rolls with diameters of 400 mm and 200 mm held at ℃, and then cooling to room temperature with a cooling roll with a diameter of 400 mm, a composition of 12μ polyethylene terephthalate layer/9μ aluminum foil/ 1
A laminated sheet of a 0μ modified polyethylene layer/60μ polyethylene blend layer was obtained.

When the peel strength between the aluminum foil and the polyethylene blend layer of this laminated sheet was measured, it was found to be 1740.
? / 1.5 (1771)

Further, when the sample was treated with boiling water in the same manner as in Example 1, no peeling between the layers and no decrease in adhesive strength were observed.

Example 7 Biaxially stretched nylon-6 film with a thickness of 15μ and a thickness of 7
μ aluminum foil was laminated using a urethane adhesive.

Next, a Zn partial salt of an ethylene-methacrylic acid copolymer with a carbonyl group concentration of 210 m-eq/100 g polymer, a melting point of 99°C, a Vicat softening point of 80°C, and a melt index of 5.0 P710m1n was used. Ionomer 60% by weight and density 0.93? 1crd, melting point is 97
℃, MIfJ: 12. oy71Qmm, 40% by weight of ethylene vinyl acetate copolymer with vinyl acetate content of 8% by weight
Using the first extruder having a screw with a diameter of 50 mm, a blend with a density of 0.925
, 60% by weight of low density polyethylene with a melting point of 121'C1MI 4.0'if710mm and a density of 0.92? /
cril, melting point 105℃, MI 8.0? /10m
A blend of 40% by weight of ethylene-vinyl acetate copolymer containing 4% by weight of In vinyl acetate was prepared with a diameter of 6511 mm.
Using a second extruder with a screw of L7ILφ,
Co-extrusion is carried out from a T-shaped two-layer double gouer with a width of 650 mm kept at a temperature of 290°C, and this molten two-layer laminate and the aluminum laminate previously heated and maintained at 100°C with an oven and an infrared heater are used. A pair of crimping rolls with diameters of 400 mm and 200 mm are held at a temperature of 90°C, and then cooled to room temperature using a cooling roll with a diameter of 400 mm, thereby forming a 15μ nylon-
A laminate sheet of 6 layers/7μ aluminum foil/15μ ionomer blend layer and 155μ polyethylene blend layer was obtained.

When the peel strength between the aluminum foil and the polyethylene blend layer of this laminated sheet was measured, it was 620?
71.5c1rL, and was a laminated material with excellent heat sealability and impact resistance.

Example 8 Maleic anhydride and methacrylic acid were added to an ethylene-propylene random copolymer with an ethylene content of 4 mol%.
:l molar ratio and the grafted carbonyl group concentration is 18
0m-eq/100g polymer, crystallinity 49%, melting point 145°C, Vicat softening point 134°C, MI 13
．． Modified propylene copolymer 7 with 0 P/l 0ynin
0% by weight, density 0.91f/C111, melting point 162
℃, a blend with 30 wt. An ethylene-propylene block copolymer with an ethylene content of 5 mol % and a diameter of 65
Using a second extruder with a mmφ screw, coextrusion was carried out through a T-shaped two-layer double die with a width of 650 mm and the temperature was maintained at 220°C, and this molten two-layer laminate was heated in an oven and high frequency. A 100 μ thick aluminum sheet with a protective film made of epoxy resin on one surface was preheated to 220°C using an induction heating device, and the aluminum sheet was heated to 200°C with diameters of 400 mm and 200 mm.
By pressing with a pair of rolls and then cooling to room temperature with a cooling roll with a diameter of 400 mm, the composition is epoxy resin protective film / 100μ aluminum sheet / 15μ modified propylene copolymer blend layer 150μ propylene copolymer layer A laminated sheet was obtained.

The peel strength between the aluminum sheet and the propylene copolymer layer of this laminated sheet was measured and was 1510.
? / 771 on 1.5.

Moreover, when the same boiling water treatment and heated steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength was observed.

Example 9 A 12μ thick biaxially stretched polyethylene terephthalate film, a 15μ thick biaxially stretched nylon 6 film, and a 9μ thick aluminum foil were laminated using a urethane adhesive.

Next, a carbonyl group concentration of 31 Om-eq/100g polymer was prepared by grafting maleic anhydride and itaconic anhydride at a molar ratio of 3:1 onto an ethylene-propylene block copolymer with an ethylene content of 5 mol%. , crystallinity is 60%
, a modified propylene copolymer 6 with a melting point of 152°C, a Vicat softening point of 139°C, and an MI of 12.0 P/10m1n.
5% by weight, density is o, c+oy/=, melting point is 154°C,
35% by weight ethylene-propylene block copolymer with MI of 10.07/10m1n, ethylene content of 5 mol%, average molecular weight of 100,000, ethylene content of 62 mol%, propylene content of 35 mol%, A blend of 5% by weight of ethylene-propylene-diene copolymer rubber (EPDM) containing 3% by mole of 1.4 oxadiene was prepared using a first extruder having a screw with a diameter of 50 mm.
Also, the density is o, 9oy, '=, the melting point is 157℃, MI
is 9.0 f710m1n, -[-tyrene content is 4
Mol% ethylene-propylene block copolymer 95
A blend of 5% by weight of EPDM and 5% by weight of the EPDM was produced using a second extruder equipped with a screw with a diameter of 65 threads, into a T-shaped two-layer double extruder with a width of 650 mm and a temperature maintained at 230°C. This molten two-layer laminate is co-extruded from aluminum, and the aluminum laminate is heated and maintained at 200°C in advance using an oven and a high-frequency induction heating device. By pressing with a pair of rolls and then cooling to room temperature with a cooling roll with a diameter of 400 mm, the following structure is obtained: 12μ polyethylene terephthalate layer/6 layers of 15μ nylon/9μ aluminum foil/15μ modified propylene copolymer blend layer/ A laminated sheet having a 45μ propylene copolymer blend layer was obtained.

The peel strength between the aluminum foil and the propylene copolymer blend layer of this laminated sheet was measured and found to be 920 g/1.5 CrrL.

Moreover, when the same boiling water treatment and heated steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength was observed.

Example 10 A biaxially stretched polyethylene terephthalate film with a thickness of 12μ and an aluminum foil with a thickness of 9μ were laminated using a urethane adhesive.

Next, the carbonyl group concentration of maleic anhydride grafted to poly4-methylpentene-1 was 120 m-eq/1.
0 (1 polymer, crystallinity 63%, melting point 231°C, M
170% by weight of modified poly-4-methylpentene with an I of 12.0 f/10 m1n and a density of 0.84 fI/c111
, poly-4 with a melting point of 235°C and an MI of s, oy/10
- A blend of 130% by weight of methylpentene was prepared by using a first extruder having a screw with a diameter of 50 mm, and the above-mentioned 190% by weight of poly-4 methylpentene, an average molecular weight of 100,000, and an ethylene content of 62 mol% , propylene content is 35 mol%, ■・4 hexadiene content is 3
Mol% of ethylene-propylene-diene copolymer (EP
DM) at a temperature of 310% by weight using a second extruder having a screw with a diameter of 65m1φ.
Co-extrusion was carried out from a T-shaped two-layer double die with a width of 650 mm kept at ℃, and this molten two-layer laminate and the aluminum laminate previously heated and held at 260 ℃ using an oven and a high-frequency induction heating device were combined. By pressing with a pair of rolls with a diameter of 400 mm and 200 mm 1 mm maintained at a temperature of 250 °C, and then cooling to room temperature with a cooling roll with a diameter of 400 mm, a 12μ polyethylene terephthalate layer/9μ was formed. Aluminum foil/15μ modified poly
4-methylpentent blend layer/60μ poly-4-
A laminate of methyl bentent blend layers was obtained.

Further, this laminated sheet was left in a heating furnace maintained at 180° C. for 6 hours.

The peel strength between the aluminum foil and the poly-4 methyl pentene blend layer of this laminated sheet was measured and found to be 807 P/1.5 cIrL.

In addition, when the sample was subjected to boiling water treatment and heated steam treatment in the same manner as in Example 1, no delamination between the layers or a decrease in adhesive strength was observed.

Example 11 A biaxially stretched polyethylene terephthalate film with a thickness of 12μ and an aluminum foil with a thickness of 9μ were laminated using a urethane adhesive.

Next, a copolymer of isotactic polypropylene grafted with acrylic acid, which is a Na partial salt, has a carbonyl group concentration of 270 m-eq/100f, and a melting point of 1.
43°C, Vicat softening point 123°C, MI 12.0
Ionomer 60% by weight of g/l Q min and density 0.90 g/-1 melting point 158°C, MI 8,0 P
/ 10 min, using a first extruder having a screw with a diameter of 50 mm, a blend of 40% by weight of an ethylene-propylene block copolymer with an ethylene content of 5 mol% was added. The block copolymer was extruded using a second extruder having a screw with a diameter of 65 mm, and a T extruder with a width of 650 mm was kept at a temperature of 23°C.
Co-extrusion is carried out from a double die for two layers, and this molten two-layer laminate is preheated for 20 minutes using an oven and high-frequency induction heating device.
The aluminum laminate heated and held at 0°C is heated to 190°C and has a diameter of 400 mm and a diameter of 200 m.
Crimp with a pair of rolls of 1φ, then rolls with a diameter of 400mm
By cooling to room temperature using a cooling roll, a laminate having a composition of 12μ polyethylene terephthalate layer/9μ aluminum foil/2oμ ionomer blend layer and 150μ propylene copolymer layer was obtained.

The peel strength between the aluminum foil and the propylene copolymer layer of this laminated sheet was measured and was 1060 f/1.
．． It was 5cIrL.

Moreover, when the same boiling water treatment and heated steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength was observed.

Example 12 A biaxially stretched polyethylene terephthalate film with a thickness of 12μ and an aluminum foil with a thickness of 9μ were laminated using a urethane adhesive.

Next, maleic anhydride was grafted onto an ethylene-propylene block copolymer with an ethylene content of 4 mol%, and the carbonyl group concentration was 130 m-eq/100 f.
A modified propylene copolymer with a crystallinity of 61%, a melting point of 154°C, a Vicat softening point of 140°C, and an MI of 10.0P/10ml was divided into two parts with a screw having a diameter of 50mmφ. An extruder for the first and third layers equipped with an adapter having branched melt channels was used, and nylon-6 with a melting point of 211° C. and a density of 1.14 g/CIrL was used with a screw having a diameter of 50 mm. the second with
Using a layer extruder, the density was 0.90 S'/Makoto, the melting point was 158°C, and the MI was 8. Of710MIn, an ethylene-propylene block copolymer with an ethylene content of 5 mol% was prepared using a fourth layer extruder having a screw with a diameter of 651 mφ, and the temperature was maintained at 240°C.
Co-extrusion is performed from a T-type 4-layer die of ix, and the temperature of this molten 4-layer laminate and the aluminum laminate, which has been previously heated and maintained at 200°C using an oven and a high-frequency induction heating device, is maintained at 190°C. A pair of rolls with a diameter of 4001 mφ and a diameter of 200 mm are used to press the rolled pieces, and then a roll with a diameter of 40 mφ is used.
By cooling to room temperature with a 0 φ cooling roll, the composition becomes 12 μ polyethylene terephthalate layer / 9 μ aluminum foil / 3 μ modified propylene copolymer layer / 15 μ
Nylon-6/3μ modified propylene copolymer layer 150μ
A laminate of propylene copolymer layers was obtained.

The peel strength between the aluminum foil and the propylene copolymer layer of this laminated sheet was measured and was 817 g/1.5.
It was cIrL.

Moreover, when the same boiling water treatment and heated steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength was observed.

Example 13 A biaxially stretched polyethylene terephthalate film with a thickness of 12μ and an aluminum foil with a thickness of 9μ were laminated using a urethane adhesive.

Next, an ethylene-propylene block copolymer with an ethylene content of 5 mol% was grafted with maleic anhydride, fumaric acid, and vinyl acetate to give a carbonyl group concentration of 250%.
m-eq/100g polymer, crystallinity 56%, melting point 151°C, Vicat softening point 140°C, MI 12
．． 70% by weight of modified propylene copolymer of 0 f/10 m1n, density of o, 9oy, '=, melting point of 162°C, MI
Using a first extruder having a screw with a diameter of 50 mm, a blend of 30 wt.・
Ethylene-propylene-diene copolymer (EPDM) 10 with 70% by weight of polypropylene, average molecular weight of 100,000, ethylene content of 62 mol%, propylene content of 35 mol%, ■・4 hexadiene content of 3 mol% weight%
A second extruder having a screw with a diameter of 501 mφ was used for the blend, and a third extruder with a screw having a diameter of 65 mφ was used for the isotactic polypropylene, and the temperature was maintained at 220°C. Drooped width 650
Co-extrusion is carried out from a 11tm T-shaped three-layer triple die, and this molten three-layer laminate and the aluminum laminate are pressed together with a pair of rolls with diameters of 400 mm and 200 mm at room temperature to prepare a preliminary. Gluing was done.

Next, this laminated sheet was main bonded using a pair of rolls with diameters of 400 @ IEφ and 200 gmφ maintained at a temperature of 200°C, and then cooled to room temperature using a cooling roll with a diameter of 400 m1cφ. A laminate of ethylene terephthalate layer/9μ aluminum foil/lOμ modified propylene copolymer binary blend layer, 150μ modified propylene copolymer ternary blend layer, 710μ isotactic polypropylene layer was obtained.

It was difficult to separate the aluminum foil and polypropylene layers of this laminated sheet, and when the sheets were subjected to boiling water treatment and heated steam treatment in the same manner as in Example 1, no separation between the layers was observed.

Example 14 A biaxially stretched polyethylene terephthalate film with a thickness of 12μ and an aluminum foil with a thickness of 9μ were laminated using a urethane adhesive.

Next, an ethylene-propylene random copolymer with an ethylene content of 4 mol% was grafted with maleic anhydride and acrylic acid, and the carbonyl group concentration was 520 m-eq/1.
0oz polymer, crystallinity 47%, melting point 143°C,
Vicat softening point is 130℃, MI is 13.0 f/I
Q-Kaku's modified propylene copolymer is 40% by weight and the density is 0.
90g/-1 melting point is 154℃, MI is 1O10g/d,
A blend of 60% by weight of an ethylene-propylene block copolymer with an ethylene content of 5% by mole and a diameter of 50%
Using a first extruder having a screw of ynmφ, 20% by weight of the modified propylene copolymer, 77% by weight of the ethylene-propylene block copolymer, an average molecular weight of 100,000, and a propylene content of 35 mol%. A blend of 3% by weight of ethylene-propylene copolymer rubber (EPR) of
Using an extruder, the blend of 95% by weight of the ethylene-propylene block copolymer and 5% by weight of the EPR was added to a third tube having a screw with a diameter of 65 ynmφ.
Width 650m kept at 220℃ using an extruder
Coextrusion was performed from a T-shaped three-layer triple die of M, to obtain a three-layer coextruded laminate.

Next, this three-layer coextruded laminate and the aluminum laminate were combined, and the diameter was 40°C while the temperature was maintained at 200°C.
After bonding with a pair of rolls of 0iiφ and 200iiφ, it was cooled to room temperature using a cooling roll with a diameter of 400iiφ, and the composition was 12μ polyethylene terephthalate layer/9.
A laminate of μ aluminum foil 15 μ modified propylene copolymer binary blend layer/10 μ modified propylene copolymer ternary blend layer 155 μ propylene copolymer binary blend layer was obtained.

When the peel strength between the aluminum foil and the propylene copolymer blend layer of this laminated sheet was measured, it was found to be 930.
g/1.5 CrrL.

Moreover, when the same boiling water treatment and heated steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength was observed.

Example 15 An ethylene-propylene block copolymer with an ethylene content of 5 mol% was grafted with maleic anhydride, fumaric acid, and vinyl acetate, and the carbonyl group concentration was 250 m-e.
q/100g polymer, crystallinity 56%, melting point 151
℃, Vicat softening point is 138℃, MI is 12.0? /
10mln modified propylene copolymer 60% by weight, density 0.90f/c11t, melting point 154°C, MI 10
．． 01/lOM, a blend with 40% by weight of an ethylene-propylene block copolymer with an ethylene content of 5 mol% was prepared using a first screw having a diameter of 50 mrILφ.
Using an extruder, 95% by weight of the ethylene-propylene block copolymer and ethylene having a density of 0, 93 fI/d, a melting point of 102°C, an MI of 8.0 f710, and a vinyl acetate content of 5% by weight were used. - A blended product with 5% by weight of vinyl acetate copolymer is extruded from a T-shaped two-layer double die with a width of 650 mm kept at a temperature of 220°C using a second extruder with a screw with a diameter of 65 itφ. perform extrusion,
This molten two-layer laminate and an aluminum foil having a thickness of 30 μm were pressed together at room temperature using a pair of rolls having diameters of 400 mm and 200 mm for preliminary adhesion.

Next, this laminated sheet was passed through an oven maintained at a temperature of 200°C for 10 seconds, and then the sheet was heated to a diameter of 200°C.
By crimping with a pair of rolls and cooling to room temperature with a cooling roll with a diameter of 400vtmφ, a laminate with a composition of 30μ aluminum foil / 10μ modified propylene copolymer blend layer / 60μ propylene copolymer blend layer was formed. Obtained.

The peel strength between the aluminum foil and propylene copolymer blend layer of this laminated sheet was measured and was 2170.
It was 1.5 CIIL/1.5 CIIL.

Moreover, when the same boiling water treatment and heated steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength was observed.

Example 16 Low density polyethylene grafted with maleic anhydride, carbonyl group concentration 70 m-eq/100 polymer, crystallinity 54%, melting point 116°C, Vicat softening point 9
Modified polyethylene 40 at 0°C, MI s, oy/io=
Maleic acid and acrylic acid are grafted to a 90% hydrolyzate of ethylene-vinyl acetate copolymer with a vinyl acetate content of 33% by weight and a carbonyl group concentration of 230% by weight.
m-eq/100g polymer, crystallinity 58%, melting point 103°C, Vicat softening point 92°C, MI 5.0P/
40% by weight of a modified ethylene copolymer of 110ff1, a melting point of 129°C, and a density of 0.955? /crA, 20% by weight of high density polyethylene with MI of 5.5-710m#r
Using a first extruder having a screw with a diameter of 501 mφ, the blended product was prepared using a second extruder having a screw with a diameter of 651 mφ, and the temperature was maintained at 290° C. This molten two-layer laminate was co-extruded from a T-shaped two-layer double die, and a 150μ thick aluminum foil whose surface had been treated with boehmite was co-extruded into a tube with a diameter of 400μ maintained at a temperature of 90°C.
Temporary adhesion was performed by pressing with a pair of rolls of iφ and 200iiφ.

Next, main adhesion was performed by passing this laminated sheet through an oven maintained at a temperature of 140° C. for 15 seconds to obtain a laminate with a composition of 150 μ aluminum foil / 20 μ modified polyethylene blend layer / 100 μ high density polyethylene layer. Ta.

The peel strength between the aluminum foil and the high-density polyethylene layer of this laminated sheet was measured and was 2850 g/1.
It was 5CrrL.

Further, when a boiling water treatment and a heated steam treatment were performed in the same manner as in Example 1, no peeling between the layers or a decrease in adhesive strength was observed.

Example 17 Ethylene-propylene with an ethylene content of 3 mol%, a random copolymer with maleic anhydride and fumaric acid grafted at a molar ratio of 3:l, and a carbonyl group concentration of 240 m-
eq/100g polymer, crystallinity 51%, melting point 14
6℃, Vicat softening point is 136℃, MI is 13.0?
/10ynin modified propylene copolymer with a diameter of 32
A first extruder having a mmφ screw was used, and the density was 0.90? /cri1, melting point 158℃, MI 8
．． (1/10mn Ethylene-propylene block copolymer with 5 mol% ethylene content and a diameter of 5011Lr
Using a second extruder with an ILφ screw, coextrusion was performed from a double die for two layers, and the composition ratio of the modified propylene copolymer layer:propylene copolymer layer was determined by the inflation method with a large Dolow ratio. A two-layer coextruded film with a total film thickness of 72μ was obtained with Gani23.

Next, this two-layer coextruded film and aluminum foil with a thickness of 18μ were combined, passed through an oven equipped with pinch rolls maintained at a temperature of 190°C for 30 seconds, and then passed through a cooling roll with a diameter of 400iiφ. By cooling to room temperature, a laminate having a configuration of 18μ aluminum foil/3μ modified propylene copolymer layer/69μ propylene copolymer layer was obtained.

The peel strength between the aluminum foil and the propylene copolymer layer of this laminated sheet was measured and was 1270? /
It was 1.5 cIfL.

Moreover, when the same boiling water treatment and heated steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength was observed.

Example 18 An ethylene-propylene random copolymer with an ethylene content of 3 mol% was grafted with maleic anhydride and fumaric acid at a molar ratio of 3:l, and the carbonyl group concentration was 240 m-
eq/100g polymer, crystallinity 51%, melting point 14
6°C, Vicat softening point is 136°C, MI is 13.0
f/10ml rt modified propylene copolymer 70% by weight
The density is 0.90P/i, the melting point is 158°C, and the MI is 8.
0 P/10ynin, a blend with 30% by weight of an ethylene-propylene block copolymer with an ethylene content of 5 mol% was prepared using a first screw having a diameter of 32 mm.
Using an extruder, the ethylene-propylene block copolymer was coextruded from a two-layer gouer using a second extruder having a screw with a diameter of 50 mm, and the thickness was increased by an inflation method. A two-layer coextruded film with a diameter of 60μ was obtained.

Next, this two-layer coextruded film and an aluminum sheet with a thickness of 100μ are combined and temporarily bonded by pressing with a pair of rolls with diameters of 400 mm and 200 mm, which are maintained at a temperature of 140 °C. I did it.

Next, by passing this laminated sheet through an oven maintained at a temperature of 230° C. for 10 seconds, the composition was changed to 100μ aluminum sheet 1−/10μ modified propylene copolymer blend layer 150μ propylene copolymer layer A laminate was obtained.

When the peel strength between the aluminum sheet and the propylene copolymer layer of this laminated sheet was measured, it was found that 1960
? /1.5 cfrL.

Moreover, when the same boiling water treatment and heated steam treatment as in Example 1 were carried out, no peeling between the layers and no decrease in adhesive strength was observed.

[Brief explanation of drawings]

FIG. 1 is an enlarged sectional view of a laminate produced by the method of the present invention. 1... Laminated sheet, 2...--aluminum foil or sheet, 3...-modified olefin resin layer, 4... crystalline olefin resin layer, heat-resistant resin layer. 5...Adhesive layer, 6...

Claims (1)

[Scope of Claims] 1. A crystalline olefin resin layer with a crystallinity of 15 to 9.
5%, carbonyl group content 1 to 600 meq/l
00? a step of co-melting extruding a modified olefin resin layer having a concentration of a polymer and having a monopolized olefin unit of the same type as the crystalline olefin resin as a multilayer structure; 1. A method for producing a laminate, comprising the step of fusing an aluminum foil or sheet in a state adjacent to the foil or sheet. 2. Prior to bringing the aluminum foil or sheet into contact with the modified olefin resin, the aluminum foil or sheet is maintained at a temperature equal to or higher than the Vicat softening point of the modified olefin resin, and the freshly extruded multilayer structure is brought into contact with the aluminum foil or sheet. Claim 1 characterized in that it is fused to a sheet.
The method described in section. 3. The freshly extruded multilayer structure is combined with the aluminum foil or sheet to produce a laminate in which the modified olefin resin is temporarily adhered to the aluminum foil or sheet, and then this laminate is combined with the modified olefin resin. The method according to claim 1, characterized in that the method is heated to a temperature equal to or higher than the Vicat softening point of. 4 The multilayer structure is formed into a film or sheet in advance, and the film or sheet and the aluminum foil or sheet are stacked so that the modified olefin resin layer faces the aluminum foil or sheet, and then the stacking is performed. The method according to claim 1, characterized in that the combined body is pressure-bonded at a temperature equal to or higher than the Vicat softening point of the modified olefin resin.